(54j) Safety Assessment of Secondary Alcohol Oxidation with Hydrogen Peroxide

Yue Sun¹, Lei Ni², Maria Papadaki³, Wen Zhu¹, Juncheng Jiang² and M. Sam Mannan¹

1 Mary Kay O’Conner Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, Texas, 77843-3122, USA

2 Jiangsu Key Laboratory of Hazardous Chemicals Safety and Control, College of Safety Science and Engineering, Nanjing Tech University, Mail Box 13, No. 200, North Zhongshan Road, 210009, Nanjing, China

3 Department of Environmental & Natural Resources Management, School of Engineering, University of Patras Seferi 2, Agrinio GR30100, Greece

+1(979)985-0919, yuesun@tamu.edu

Abstract

Ketones are produced on massive scale in industry as solvents, polymer precursors, and pharmaceuticals. Current ways of producing ketone through alcohol dehydrogenation are energy intensive and usually expensive, hazardous and toxic due to employing strong oxidizing agents. In 1997, Kazuhiko Sato, et al., found a way of producing ketones via 30 % hydrogen peroxide oxidation of alcohol, and tungstate as catalyst along with a phase transfer catalyst. This method is considered as ‘green chemistry’ since it is organic solvent- and halide-free. A great deal of laboratory work was subsequently done focusing on different catalysts and experimental conditions as well as their effects on yields of different ketones.

However, there are safety concerns for scale-up regarding this reaction system because of its runaway potential. Thus, the purpose of this work is to conduct a comprehensive study of thermal and kinetic behavior of this reaction system. Calorimeters, such as DSC, Phi-TEC and RC1e, are used to help study, experimentally and theoretically, these reactions under normal operating and runaway conditions. In this paper, we report thermal hazard assessment of these reactions and discuss their classification according to Stoessel criticality diagram. Moreover, the influence of stirring rate on reaction heat generation is discussed. The findings will be further used to propose measures for safer design and scale-up of this reaction process in order to avert a potential runaway.

Keywords

Thermal runaway, safety assessment, hydrogen peroxide, secondary alcohol oxidation, calorimeter